Citation: Maoxiang Zhou, Man Yang, Xiaofeng Yang, Xiaochen Zhao, Lei Sun, Weiqiao Deng, Aiqin Wang, Jun Li, Tao Zhang. On the mechanism of H₂ activation over single-atom catalyst: An understanding of Pt₁/WO_x in the hydrogenolysis reaction[J]. Chinese Journal of Catalysis, ;2020, 41(3): 524-532. doi: S1872-2067(19)63517-5 shu

On the mechanism of H₂ activation over single-atom catalyst: An understanding of Pt₁/WO_x in the hydrogenolysis reaction

Maoxiang Zhou ^a,c, ,
Man Yang ^a,c ,
Xiaofeng Yang ^a ,
Xiaochen Zhao ^a ,
Lei Sun ^d ,
Weiqiao Deng ^d ,
Aiqin Wang ^a,b ,
Jun Li ^e ,
Tao Zhang ^a,b

a CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
c University of Chinese Academy of Sciences, Beijing 100049, China;
d State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
e Department of Chemistry and Key Laboratory of Organic Optoelectronics&Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084, China

Received Date: 20 August 2019
Revised Date: 20 September 2019

Fund Project: This work was supported by the National Key R&D Program of China (2018YFB1501602 and 2016YFA0202801), the National Natural Science Foundation of China (21690080, 21690084, 21673228, 21721004, 21776269, and 21606227), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), and Dalian National Laboratory for Clean Energy (DNL180303).

Owing to the atomic dispersion of active sites via electronic interaction with supports, single-atom catalysts (SACs) grant maximum utilization of metals with unique activity and/or selectivity in various catalytic processes. However, the stability of single atoms under oxygen-poor conditions, and the mechanism of hydrogen activation on SACs remain elusive. Here, through a combination of theoretical calculation and experiments, the stabilization of metal single atoms on tungsten oxide and its catalytic properties in H₂ activation are investigated. Our calculation results indicate that the oxygen defects on the WO₃(001) surface play a vital role in the stabilization of single metal atoms through electron transfer from the oxygen vacancies to the metal atoms. In comparison with Pd and Au, Pt single atoms possess greatly enhanced stability on the WO_x(001) surface and carry negative charge, facilitating the dissociation of H₂ to metal-H species (H^δ-) via homolytic cleavage of H₂ similar to that occurring in metal ensembles. More importantly, the facile diffusion of Pt-H to the WO_x support results in the formation of Brønsted acid sites (H^δ+), imparting bifunctionality to Pt₁/WO_x. The dynamic formation of Brønsted acid sites in hydrogen atmosphere proved to be the key to chemoselective hydrogenolysis of glycerol into 1,3-propanediol, which was experimentally demonstrated on the Pt₁/WO_x catalyst.
- Single-atom catalyst,
- Pt,
- Density function theory,
- Hydrogen dissociation,
- Tungsten oxide
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On the mechanism of H₂ activation over single-atom catalyst: An understanding of Pt₁/WO_x in the hydrogenolysis reaction